JPS6326757B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a substituted acetate anilide compound, a method for producing the compound, and a herbicide containing the compound as an active ingredient. More specifically, the substituted acetate anilide compound of the present invention has the general formula: [In the formula, X represents an oxygen atom or a sulfur atom, and Y and Z represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. (Here, one of Y and Z necessarily represents a hydrogen atom, and the other does not represent a hydrogen atom.)] The compound of the above general formula () can be produced by the following method, and the present invention also relates to the production method. That is, the general formula: (In the formula, X is the same as above. Hal represents a halogen atom.) 2-halogenbenzazole represented by the general formula: (In the formula, Y and Z are the same as above. M represents a hydrogen atom or an alkali metal atom.) A substituted acetate anilide compound represented by the general formula (), characterized by reacting with a compound represented by the following: manufacturing method. Furthermore, the present invention also relates to a herbicide containing the substituted acetic acid anilide compound of the general formula () as an active ingredient. In Japanese Patent Application Publication No. 154762 of 1972, the general formula (wherein n represents 1, 2, 3 or 4, each R individually and mutually separately hydrogen, halogen, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy, alkylthio, halogenoalkylthio, amino, alkylamino, represents dialkylamino, nitro, cyano or alkoxycarbonyl, and the two radicals R together can also represent a methylenedioxy, dichloromethylenedioxy or difluoromethylenedioxy group, R ¹ represents hydrogen or alkyl, R ² and R ³ are the same or different and individually hydrogen or alkyl,
refers to alkenyl, alkynyl, aralkyl, cycloalkyl, aryl or nitrogen-containing heterocyclic groups, which groups may be optionally substituted in each case or, together with the nitrogen atom to which they are attached, optionally may be substituted or unsubstituted, optionally partially unsaturated, and may optionally further contain one or more heteroatoms. and optionally benzo-fused to form a monocyclic or bicyclic group, where X represents oxygen or sulfur) is described as having herbicidal activity. . As a result of further in-depth research and examination of the above-mentioned substituted carboxylic acid amide-based compounds, the present inventors have found that the substituted acetate anilide-based compound of the present compound represented by the above general formula () is completely unexpected from other related compounds. It was discovered that it has surprising herbicidal activity. Although the substituted acetic acid anilide compound of the present invention represented by the above general formula () is conceptually included in the substituted carboxylic acid amide of the above general formula (), there is no description of the compound of the present invention in the publication. can not see. As is clear from the general formula (), the compound of the present invention has an acetic acid anilide skeleton, and the carbon atom at the α-position of the acetic acid residue is substituted with a benzothiazol-2-yloxy group or a benzoxazol-2-yloxy group. , and is characterized by having a halogen atom or an alkyl group substituted at the 3rd or 4th position of the phenyl group among the N-methylanilide residues, and compared to similar compounds described in the publication. These findings are completely unexpected, as they also have extremely specific herbicidal effects. The compounds of the present invention have low toxicity to warm-blooded animals and good selectivity to cultivated plants, that is, they do not harm cultivated plants at normal concentrations, so they can be used as herbicides for weed control. It can be conveniently used for The herbicide of the present invention exhibits superior selective control efficacy, particularly when used as a pre-emergence soil treatment agent for paddy field weeds, or as a foliage and soil treatment agent. As described above, the compound of the present invention is excellent in safety, exhibits outstanding herbicidal activity, and has a wide herbicidal spectrum. For example, paddy field weeds include: Botanical name Latin name Dicotyledonous plant Rotala indica Koehne Azena Lindernia Procumbens
Philcox Ludwiga prostrata Roxburgh Potamogeton distinctus A.
Benn Chickweed Elatine triandra Schk Monocot Echinochlon erus−galli
Beauv.var Monochoria vaginalis Presl Eleocharis acicularis L. Eleocharis, Kuroguwai
Ohwi Cyperus diffoumis L. Cyperus serotinus Rottboel Sagittaria pygmaea Miq Alisma canaliculatum A.Br.
et Bouche Firefly Soirpus juncoides Roxburgh
var., etc., and has the characteristic that it has no harmful effect on paddy rice. In addition, as upland weeds, for example, Botanical name: Latin name: Dicotyledonous Polygonum sp. Chenopodium album
Linnaeus Chickweed Stellaria media Villars Portulaca oleracea Linnaeus Monocot Millet Echinochlca erus−galli
Beauv.var. Digitaria adscendens Henr. Cyperus iria L. has herbicidal activity, and has the characteristic that it has no harmful effects on the following crops. For example, dicotyledonous plants include mustard, mustard, cotton, carrot, legumes, potato, beet, and citrus. Examples of monocotyledonous plants include corn, rice, oats, barley, wheat, millet, and sugar cane. However, the above-mentioned plant types should be considered to be representative examples of the genus given by its Latin name. However, the adaptability of the active compound of the present invention is not limited only to weeds in paddy fields and upland fields, but is also effective against weeds harmful to rushes, etc., and weeds in fallow land, etc. be. The word weed here means in its broadest sense any plant that grows in undesirable locations. The substituted acetate anilide compound represented by the general formula () of the present invention is synthesized by the following general method. (In the formula, X, Y, Z, Hal and M are the same as above.) In the above reaction formula, X is specifically an oxygen atom or a sulfur atom, Y
and Z is a hydrogen atom, a halogen atom such as fluoro, chlorine, bromo, iodine, methyl, ethyl,
n-(or iso-)propyl, n-(iso-, sec
-, or tert-) having 1 to 4 carbon atoms such as butyl
represents an alkyl group. In the method for producing a compound of the general formula () shown in the above reaction formula, the general formula () which is a raw material
Specific examples of the 2-halogenobenzazole include 2-chlorobenzothiazole and 2-chlorobenzoxazole, and also 2-bromo-form in place of 2-chloro-form. Further, at the same time, the compound of general formula () which is a raw material is specifically 3'-chloro-N-methylhydroxyacetic acid anilide, 4'-chloro-N-methylhydroxyacetic acid anilide, 3'-fluoro-N-methylhydroxyacetic acid anilide. 4'-Fluoro-N-methylhydroxyacetic acid anilide 3'-Bromo-N-methylhydroxyacetic acid anilide 3'-Methyl-N-methylhydroxyacetic acid anilide 4'-Methyl-N-methylhydroxyacetic acid anilide 3'-ethyl-N -Methylhydroxyacetic acid anilide Mention may be made of 4'-isopropyl-N-methylhydroxyacetic acid anilide, and also their alkali metal salts. Next, the above manufacturing method will be specifically explained using representative examples. The method of the invention is preferably carried out using a solvent or diluent. All inert solvents and diluents can be used for this purpose. Such solvents or diluents include water, aliphatic cycloaliphatic and aromatic hydrocarbons (which may optionally be chlorinated), such as hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene. , methylene chloride,
Chloroform, carbon tetrachloride, ethylene chloride and trichloroethylene, chlorpenzene; other ethers such as diethyl ether, methyl ethyl ether, di-iso-propyl ether, dibutyl ether, propylene oxide dioxane, tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, Methyl-iso-
Propyl ketone, methyl-iso-butyl ketone;
Nitriles such as acetonitrile, propionitrile, acrylonitrile; alcohols such as methanol, ethanol, iso-propanol, butanol, ethylene glycol; esters such as ethyl acetate, amyl acetate; acid amides such as dimethylformamide, dimethylacetamide; Mention may be made of sulfones, sulfoxides such as dimethyl sulfoxide, sulfolane; and bases such as pyridine. Further, as described above, the reaction of the present invention can be carried out in the presence of an acid binder. Such acid binders include commonly used alkali metal hydroxides, carbonates, bicarbonates, alcoholates, etc., and tertiary amines such as triethylamine, diethylaniline, pyridine, etc. . The method of the invention can be carried out within a wide temperature range. It is generally carried out between -20°C and the boiling point of the mixture, preferably between 0 and 100°C. Further, although it is preferable to carry out the reaction under normal pressure, it is also possible to operate under increased pressure or reduced pressure. When the compound of the present invention is used as a herbicide, it can be used directly as it is after being diluted with water, or it can be used in various formulations using agricultural chemical adjuvants by methods commonly used in the agricultural chemical manufacturing field. can do. In actual use, these various formulations can be used directly or diluted with water to a desired concentration. Agrochemical auxiliaries referred to here include, for example, diluents (solvents, extenders, carriers), surfactants (solubilizers, emulsifiers, dispersants, humectants), stabilizers, fixing agents, propellants for aerosols, co-agents, etc. Examples include stimulants. Solvents include water: organic solvent; hydrocarbons [e.g., n-hexane, petroleum ether, naphtha, petroleum fractions (paraffin wax, kerosene, light oil, medium oil, heavy oil), benzene, toluene, xylenes], halogenated Hydrocarbons [e.g. chlormethylene, carbon tetrachloride, trichlorethylene, ethylene chloride, ethylene dibromide, chlorobenzene chloroform], alcohols [e.g. methyl alcohol, ethyl alcohol, propyl alcohol, ethylene glycol], ethers , [e.g. ethyl ether, ethylene oxide, dioxane],
Alcohol ethers, [e.g., ethylene glycol monomethyl ether, etc.], ketones, [e.g., acetone, isophorone, etc.], esters, [e.g., ethyl acetate, amyl acetate, etc.], amides, [e.g., dimethylformamide, dimethylacetamide, etc.] ], sulfoxides [for example, dimethyl sulfoxide, etc.]. Inorganic granules as fillers or carriers; sulfur, slaked lime, magnesium lime, gypsum, calcium carbonate, silica, perlite, pumice, calcite, diatomaceous earth, amorphous silicon oxide, alumina, zeolite,
Clay minerals (e.g. pyrophyllite, talc, montmorillonite, beidellite, vermiculite, kaolinite, mica): vegetable powder; grain flour;
Starch, modified starch, sugar, glucose, crushed plant stems: synthetic resin powder; phenolic resin, urea resin, vinyl chloride resin. Examples of surfactants include anionic surfactants; alkyl sulfates, [e.g., sodium lauryl sulfate, etc.], arylsulfonic acids, [e.g., alkylarylsulfonates, sodium alkylnaphthalenesulfonates], and succinates. , polyethylene glycol alkylaryl ether sulfate salts: cationic surfactants; alkylamines, [e.g.
laurylamine, stearyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride, etc.], polyoxyethylene alkylamines: nonionic surfactants; polyoxyethylene glycol ethers, [e.g., polyoxyethylene alkylaryl ether, and condensates thereof ], polyoxyethylene glycol esters, [e.g., polyoxyethylene fat-proofing ester], polyhydric alcohol esters, [e.g., polyoxyethylene sorbitan monolaurate], ampholytic surfactants, etc. can. In addition, stabilizers, fixing agents [e.g., agricultural soap, caseinate lime, sodium alginate, polyvinyl alcohol (PVA), vinyl acetate adhesives, acrylic adhesives], propellants for aerosols [e.g.
Trichlorofluoromethane, dichlorofluoromethane, 1,2,2-trichloro-1,1,2-trifluoroethane, chlorobenzene, LNG, lower ether]: Potency extender: Dispersion stabilizer [e.g.
Casein, tragacanth, carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA)]: synergists can be mentioned. The compound of the present invention can be manufactured into various formulations by methods generally practiced in the agricultural chemical manufacturing field. Examples of formulation forms include emulsions, oils, wettable powders, aqueous solutions, suspensions, powders, granules, powders, capsules, and the like. The compound of the present invention contains the active ingredient in an amount of 0.001 to 100%.
It can be contained in an amount of 0.005 to 95% by weight. In actual use, the various formulations and spray preparations described above (ready-to-use)
The active compound content in the preparation is generally
A range of 0.01 to 95% by weight, preferably 0.05 to 60% by weight is suitable. The content of these active ingredients can be appropriately changed depending on the form of the preparation, the method of application, purpose, timing, location, and weed growth status. The compound of the present invention may also be used, if necessary, with other agricultural chemicals, such as insecticides, fungicides, acaricides, nematicides, antiviral agents, herbicides, plant growth regulators, attractants [e.g. Organic phosphoric acid ester compounds, carbamate compounds, dithio (or thiol)
Carbamate compounds, organic chlorine compounds, dinitro compounds, organic sulfur or metal compounds, antibiotics, substituted diphenyl ether compounds, urea compounds, triazine compounds] or/and fertilizers can also be present. Various formulations or ready-to-use preparations containing the active ingredients of the invention are available.
Preparation) refers to the application methods commonly used in the field of agrochemical manufacturing, such as spraying, misting, atomizing, dusting, powdering, water surface application, and pouring. ]: Soil application [for example, soil mixing, sprinkling, etc.]. It can also be used by so-called ultra-low-volume spraying methods. In this way it is possible to have 100% active ingredient content. The application rate per unit area is between 0.1 and 10 kg of active compound per hectare, preferably between 0.5 and 3 kg.
is used. However, in special cases it is possible, and sometimes even necessary, to exceed or fall below these ranges. The present invention comprises a compound of the general formula () as an active ingredient, and further contains a diluent (solvent and/or filler and/or carrier) and/or surfactant, and if necessary, a stabilizer, a fixing agent, etc. , a herbicidal composition comprising a synergist is provided. Furthermore, the present invention applies the compound of the general formula () to weeds and/or their locations alone or in the presence of a diluent (solvent and/or filler and/or carrier) and/or surfactant, and if necessary, For example, a weed control method is provided in which the compound is applied in combination with a stabilizer, a fixing agent, or a synergist. EXAMPLES Next, the content of the present invention will be specifically explained with reference to Examples, but the present invention should not be limited thereto. Example 1 (Wettable powder) Compound No. 1 of the present invention, 15 parts, mixture of powdered diatomaceous earth and powdered clay (1:5), 80 parts, sodium alkylbenzenesulfonate, 2 parts, sodium alkylnaphthalenesulfonate formalin condensation thing,
Three parts were ground and mixed to form a wettable powder. This is diluted with water and sprayed to kill weeds and/or where they grow. Example 2 (Emulsion) Compound No. 2 of the present invention, 15 parts, methyl ethyl ketone
70 parts of polyoxyethylene alkyl phenylethene, 8 parts of calcium alkylbenzenesulfonate were mixed and stirred to form an emulsion. This is diluted with water and sprayed onto weeds and/or their growing areas. Example 3 (Powder) 2 parts of Compound No. 3 of the present invention and 98 parts of powdered clay were pulverized and mixed to prepare a powder. This is sprinkled on weeds and/or their growing areas. Example 4 (Powder) 1.5 parts of Compound No. 4 of the present invention, 0.5 parts of isopropyl hydrogen phosphate (PAP), and 98 parts of powdered clay are ground and mixed to make a powder, and the powder is sprinkled on weeds and/or their growing areas. . Example 5 (Granules) To a mixture of 10 parts of the present compound No. 5, 30 parts of bentonite (montmorillonite), 58 parts of talc, and 2 parts of lignin sulfonate, 25 parts of water was added. By using an extrusion type granulator, 10
Form into granules of ~40 mesh and dry at 40-50°C to make granules. Sprinkle this on weeds and/or their growing areas. Example 6 (Granules) Clay mineral particles with a particle size distribution of 0.2 to 2 mm, 95
5 parts of Compound No. 6 of the present invention dissolved in an organic solvent was sprayed onto the mixer and dried at 40 to 50°C to form granules. Sprinkle this on weeds and/or their growing areas. When compared with active compounds of similar structure and of similar active form already known from the literature, the compounds of the invention demonstrate a substantially improved efficacy and a significantly reduced toxicity to warm-blooded animals. It is characterized by a low molecular weight, and therefore the compound has very high utility value. The unexpected superiority and remarkable efficacy of the active compounds according to the invention can be seen from the following test results when used against various weeds. Test Example 1 Preparation of test compound for control test (field test) by application to paddy field weeds in flooded sewage. diameter by the usual granulation method using a granulator.
It was granulated into rod-shaped particles of 0.5 mm and length of 1 to 3 mm. Composition ratio (total 100 parts) Active compound: 0.8 to 10 parts Polyoxyethylene alkyl phenyl ether:
2.5 parts bentonite: 30 parts talc: 57.5 to 66.7 parts (adjust the amount of active substance by increasing or decreasing the amount of talc). Test method (1) Chemical treatment before transplanting paddy rice The test field was plowed to a depth of 20 to 25 cm using a tractor according to the usual paddy rice cultivation method. Immediately after plowing, from the irrigation canal to a depth of 1~
We filled the area with water to a depth of 2 cm and performed the first plowing.
One to two days after the first puddling, the final puddling was carried out by flooding the area with water to a depth of approximately 5 cm. Final generation oyster 2
After a day, the field was divided into 20 m ² (2 m x 10 m) sections using hard plastic sheets. Thereafter, the compound prepared as described above was applied in water. Three days after applying the chemical, rice seedlings (variety: Kinnanpu) were grown in special seedling boxes using a powered rice transplanter.
15 days old seedlings, leaf age 2-2.5 leaves, plant height 15-17 cm)
Three to five plants were transplanted per plant. After transplantation, the water depth in the field was maintained at 3 to 5 cm, and 4 weeks after the chemical application, the control effect was investigated according to the criteria described below. (2) Chemical treatment after transplanting paddy rice The method described in Test Method (1) was used until the final plowing. Two days after the final plowing, the water depth in the field was adjusted to 2 to 3 cm, and the paddy rice was transplanted using a power rice transplanter in the same manner as in Test Method (1) above. Immediately after transplantation, use a hard plastic sheet for 20
The field was divided into sections of m ² (2 m x 10 m), and the water depth in the field was maintained at 3 to 5 cm for a long period of time. Seven days after transplanting paddy rice, the compound prepared as above was applied in water. According to the late standard, 4 weeks after drug application,
The pest control effect was investigated. Evaluation of effectiveness is as follows when compared to untreated area: 5: Weed killing rate over untreated area 95% or more (death) 4: 〃 80% or more but less than 95% 3: 〃 50% or more but less than 80% 2: 〃 30% or more Less than 50% 1: 〃 10% or more and less than 30% 0: 〃 Less than 10% (no effect) Evaluation of phytotoxicity to rice "0" indicates no phytotoxicity. The test results are shown in Table 1.

【table】

[Table] Next, a synthesis example will be shown and the method for producing the compound of the present invention will be specifically described. Synthesis example 1 1.7 g of 2-chlorobenzothiazole is added dropwise to a solution of 0.75 g of potassium hydroxide powder and 2.0 g of 3'-methyl-N-methylhydroxyacetic acid anilide while maintaining the temperature at 20°C. Warm the reaction solution to 40°C and stir at the same temperature for 2 hours. After cooling, the reaction solution was poured into water,
The precipitated crystals were separated and recrystallized from ethanol:water to obtain 2.8 g of the desired product, benzothiazol-2-yloxyacetic acid N-methyl-3-methylanilide, in the form of white crystals. mp: 129-130°C Table 2 shows the compounds of the present invention synthesized by a method substantially similar to the above.

【table】

【table】

Claims (1)

[Claims] 1. General formula: [In the formula, X represents an oxygen atom or a sulfur atom, and Y and Z represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. (Here, one of Y and Z always represents a hydrogen atom, and the other does not represent a hydrogen atom.)] A substituted acetate anilide compound represented by: 2 General formula: (In the formula, X represents an oxygen atom or a sulfur atom, and Hal represents a halogen atom.) 2-halogenbenzazole represented by the general formula: [In the formula, Y and Z are hydrogen atoms, halogen atoms,
or an alkyl group having 1 to 4 carbon atoms (wherein, one of Y and Z always represents a hydrogen atom, and the other does not represent a hydrogen atom); M represents a hydrogen atom or an alkali metal atom; ] General formula characterized by reacting with a compound represented by: (In the formula, X, Y and Z are the same as above.) A method for producing a substituted acetate anilide compound represented by the following. 3 General formula: [In the formula, X represents an oxygen atom or a sulfur atom, and Y and Z represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. (Here, one of Y and Z always represents a hydrogen atom, and the other does not represent a hydrogen atom.)] A herbicide containing a substituted acetate anilide compound represented by the following as an active ingredient.